Monoazo dyestuffs containing a benzthiazolyl radical

ABSTRACT

THE INVENTION RELATES TO AN AZO DYESTUFF THAT IS FREE FROM ACIDIC GROUPS IMPARTING SOLUBILITY IN WATER AND HAS THE FORMULA   2-(B-N=N-),3-(R&#39;&#39;(N-1)),3-((-)Y(N-1)),(A-O-SO2-),R-   BENZOTHIAZOLIUM   IN WHICH A REPRESENTS AN ARYL RESIDUE, R REPRESENTS A HYDROGEN ATOM OR AN ORGANIC RESIDUE, N=1 OR 2, R&#39;&#39; REPRESENTS AN ALKYL OR RALKYL GROUP, Y-REPRESENTS AN ANION AND B REPRESENTS THE RESIDUE OF A COUPLING COMPONENT.

United States Patent fice 3,68,162 Patented Aug. 22, 1972 MONOAZO DYESTUFFS CONTAINING A BENZTHIAZOLYL RADICAL Klaus Artz, Muttenz, Switzerland, assignor to Ciba-Geigy AG Mutteuz, Switzerland No Drawing. Filed Jan. 22, 1970, Ser. No. 5,159 Claims priority, applicafigngS/zvitzerland, Jan. 24, 1969,

Int. c1. (30% 29/08 US. Cl. 260-158 9 Claims ABSTRACT OF THE DISCLOSURE The invention relates to an azo dyestuft thatis free from acidic groups imparting solubility in water and has the formula in which A represents an aryl residue, R represents a hydrogen atom or an organic residue, n=1 or 2, R represents an alkyl or aralkyl group, Y- represents an anion and B represents the residue of a coupling component.

This invention provides new and valuable azo dyestuffs that are free from acidic groups imparting solubility in water and have the formula The group A may be an aryl residue of the naphthalene or preferably the benzene series that may carry substituents. The preferred substituents are principally those of the first order, by which is means substituents that direct a new substituent entering the benzene nucleus into paraor ortho-position in electrophilic substitution. The bond joining such substituents to the aromatic nucleus has a dipole moment which is greater than a Debye unit, the positive end of the dipole being attached to the aromatic ring. substituents of the kind specified generally have sigma values that are not greater than 0.25 (cf. Jaffe, Chem. Reviews, vol. 53, pages 219-233 [1953]). The individual substituents are as follows: alkyl, alkoxy, cycloalkyl, phenyl, ureido and acyl groups, acyl being the term used to cover organic residues obtained by removing an OH group from an organic acid, for example a carboxylic acid, sulphonic acid, carbonic acid semi-ester or carbamic acid.

The following are examples of groups that are aryl residue A can carry: methyl, isopropyl, tert.butyl, isooctyl, ethoxy, butoxy, cyclopentyl, cyclohexyl, phenyl, dimethylaminomethyl, diethylamino, phenoxy, acetylamino, butyrylamino, benzoylamino, butoxycarbonylamino, ethyloxycarbonylamino and butylaminocarbonylamino residues. Phenylazo residues may also be mentioned.

The preferred dyestuffs are those of the formula .A-O-SOz in which A, R, Y, n, R and R have the meanings given above and each of the residues 0' and d represents a hydrogen atom or a methyl, ethyl, methoxy, ethoxy, phenylthio or phenoxy residue.

In addition to the groups specified above, the group 0' can also represent a chlorine or a bromine atom, a trifluoromethyl group or an acylamino group that may be alkylated, preferably methylated, at the nitrogen atom, in which group the acyl residue is the residue of an organic monocarboxylic acid, an organic monosulphonic acid, for example methane-, ethane or para-toluenemonosulphonic acid, or the residue of a carbamic acidor a carbonic acidmonoester, for example phenoxycarbonyl, methoxycarbonyl and aminocarbonyl.

The groups R and R may be lower alkyl groups, that is to say, alkyl groups having 1 to 3 carbon atoms and that contain at least one negative substituent, that is to say, substituted methyl, ethyl, n-propyl or iso-propyl groups, for example benzyl or ,B-phenylethyl groups, halogenated alkyl groups, for example p-chloroethyl, ,B,fi,fi-trifiuoroethyl and fifY-dlChlOI'OPIOPYl groups, as well as fi-cyanoethyl and fl-cyanoethoxyethyl groups, alkoxyalkyl groups, for example fi-ethoxyethyl or B-methoxybutyl, or 'y-carbo-(methoxyor ethoxy)-propyl groups; acylaminoalkyl groups, for example, [3-(acetylor formyl)-aminoethyl groups; fatty acid acyloxyalkyl groups, for example 6- formyloxyethyl, B-acetyloxyethyl, ,8,- -diacetoxypropyl, vbutyryloxypropyl groups; fl-arylsulphonylalkyl groups, for example ,B-phenylsulphonylethyl, fi-(para-toluenesulphonyl)-ethyl groups; alkyl or arylcarbamoyloxyalkyl groups, for example p-methylcarbamyloxyethyl and B-phenylcarbamyloxyethyl groups; alkyloxycarbonylalkyl groups, for example [i-(methoxyethoxyor isopropyloxy)-carbonyloxyethyl, -y-acetamidopropyl, 13- (para-nitrophenoxy)-ethyl, B (para-hydroxyphenoxy)-ethyl, ,8 (,8'-acetylethoxycarbonyl)-ethyl, B-[(fl'-cyano-, hydroxy-, methoxyor acetoxy-) ethoxycarbonyl]-etl1yl-, B-carboxylethyl, B-a'cetylethyl, B-diethylaminoethyl, fl-cyanoacetoxyethyl, j8-benzoyl and B-(para-alkoxyor phenoxybenzoyl) oxyethyl groups. The groups R and R generally contain not more than 18 carbon atoms.

The new dyestuffs may be obtained by diazotizing a benzthiazolyl-Z-amine of the formula in which A represents an aryl residue that may be substituted and X represents a sulphur atom or preferably an oxygen atom, coupling with a coupling component H-B and, if necessary, quaternating the dyestulT obtained With an alkylating agent.

The aryloxysulphonylbenzthiazolyl 2 amines used as starting materials, and particularly the 6-aryloxysulphonyl derivatives, may be obtained by reacting a thioor preferably a hydroxy-aryl compound with para-nitrobenzenesulphochloride, reducing the para-nitrobenzenesulphonate to an amine, thiocyanating the para-aminobenzenesulphonic acid ester in orthoposition to the amino group and then condensing to form the benzthiazolyl-Z-amine.

An alternative method is to convert Z-mercaptobenzthiazoles into 2-alkylthioethers, sulphochlorinate the benzene nucleus, react the sulphochlorides with phenols and then aminate the aryloxysulphonylbenzthiazolyl-Z-alkylthioethers in 2-position with liquid ammonia.

The following compounds are examples of suitable diazo components having a benzthiazolyl residue:

2-amino-6-phenyloxysulphonylbenzthiazole,

2-amino-6- (4'-carbethoxyphenyloxysulphonyl) -benzthiazole,

2- amino-6- 3 '-methylphenyloxysulphonyl) -b enzthiazole,

2-amino-6- 3 '-methoxyphenyloxysulphonyl) -benzthiazo1e,

2-amino-6- (2-chlorophenyloxysulphonyl -benZthiaz0le,

2-amino-6- 3 '-trifiuoromethylphenyloxysulphonyl) benzthiazole,

2-amino-6- (4-methyl-Z-nitrophenyloxysulphonyl) -benzthiazole,

2-amino-6- (4'-cyanophenyloxysulphonyl) -benzthiazo1e,

2-amino-6- (4-acetaminophenyloxysulphonyl) -benzthiazole,

2-amino-6- (3 '-dimethylaminophenyloxysulphonyl benzthiazole,

2-amino-6- (4'-acetylphenyloxysulphonyl -benzthiazole,

2-amino-6- (4'-cyanoethylphenyloxysulphonyl) -benzthiazole,

2-amino-6- (B-naphthyloxysulphonyl) -benzthiaz0le,

2-amino-6- (4'-nitrophenylmercaptosulphonyl) -benzthiazole, and

2-amino-6- (4-phenylphenyloxysulphonyl) -benzthiazole.

4 Any desired coupling component can be used in the manufacture of the azo dyestuffs, for example, coupling components of the benzene or naphthalene series or those of the heterocyclic series. Coupling components of the benzene series that may be mentioned in addition to the phenols, for example metaor para-cresol, resorcinol and 1-hydroxy-3-cyanomethylbenzene, are in particular, the

aminobenzenes, for example,

aniline,

3-methylaniline,

Z-methoxy-S-methylaniline,

3-acetylamino-l-aminobenzene,

N-methylaniline,

N,B-hydroxyethylaniline,

N,fl-methoxyethylaniline,

N,fl-cyanoethylaniline,

N,/8-chloroethylaniline,

dimethylaniline,

diethylaniline,

N-methyl-N-(benzylor B-phenylethyD-aniline,

N-n-butyl-N-B-chloroethylaniline,

N-(methyl-, ethyl-, propylor butyl-)-N-;3-cyanoethylaniline,

N-methyl-N-fl-hydroxyethylaniline,

N-ethyl-N 8-chloroethylaniline,

N-methyl-N-fl-acetoxyethylaniline,

N-ethyl-N-fl-methoxyethylaniline,

N 3-cyanoethyl-N-fl-chloroethylaniline,

N-cyanoethyl-N-(acetoxyor benzoyloxyethyl)- aniline,

N,N-di-a-hydroxyethylaniline,

N,N-di-fl-acetoxyethylaniline,

N-ethyl-N,2-hydroxy-3-chloropropylaniline,

N,N-di-fl-cyanoethylaniline,

N,N-di-fi-cyanoethyl-3-methy1aniline,

N-,ti-cyanoethyl-N-/8"-hydroxyethyl-3-chloroaniline,

N,N-di-fl-cyanoethyl-3-methoxyaniline,

N,N-dimethyl-3-acetylaminoaniline,

N-ethyl-N-B-cyanoethyl-3-aeetylaminoaniline,

N,l I-di-pI-cyanoethyl-Z-methoxy-S-acetylaminoaniline,

N-methyl-N-phenacylanilines,

N-fl-cyanoethyl-Z-chloroaniline,

N,N-diethyl-3-trifluoromethylaniline,

N-ethyl-N-phenylaniline,

diphenylamine,

N-methyldiphenylamine,

N-methyl-4-ethoxydiphenylamine or N-phenylmorpholine, and

also in the amines of the formula I NHCOR;

in which R, and RC, have the meanings given above.

Valuable results can also be obtained with coupling components of the formulae CHzCHgOCHzCHaCN and in which R has the meaning given above and X represents an acylamino group, and in which alkyl represents, for example, a methyl, ethyl or propyl group.

The following coupling components are given as examples:

OOHa

NHOOCHa OC H NHoHo l C ZG Q C C S NHCOCHQ NHGOGH:

OCH:

NHCO CH3 I IHCOCHa OCH:

NHCH2CH2OO OCH NHCOCHa OCH:

NHCO 002115 NHC O CHiCHa Coupling components of the naphthalene series, especially naphthols and aminonaphthalenes, are as follows:

a-naphthol,

B-naphthol,

4-methoxy-1-hydroxynaphthalene,

Z-hydroxy-8-methylsulphonylaminonaphthalene,

2-hydroxynaphthalene-3-carboxylic acid anilide,

2-hydroxy-8-acetylaminonaphthalene,

1-hydroxynaphthalene-3-sulphonemethyleneether-4,

2-hydroxynaphthalene-6-sulphonamide,

2-hydroxynaphthalene--sulphonic acid dimethylamide,

l-hydroxy-S,8-dichloronaphthalene,

N,;9-dimethylaminoethyl-2 hydroxynaphthalene-3- carboxylic acid amide and also 1- or 2-naphthylamine,

2-phenylaminonaphthalene,

l-dimethylaminonaphthalene or 2-ethylaminonaphthalene.

Examples of heterocyclic coupling components are indoles having acidic hydrogen atoms, for example:

pyrimidines, for example, barbituric acid; and also 1,3- indandione, 1,8-naphthindandione, dimedone, acetoacetic acid anilide, meta-hydroxy-N,N-diethylaniline, S-hydroxy- 4'-methyldiphenylamine, hydroquinone-monomethylether, acetylacetone, S-hydroxybenzthiazole and 1,2-diphenylpyrazolidine-3,5-di0ne and finally, coupling components of the aniline series, for example, 1,2,3,4-tetrahydroquinolines (known as tetrahydroquinolines) and benzomorpholines, for example, tetrahydroquinoline, N-fl-cyanoethylor N-B-hydroxyethyltetrahydroquinoline, N-Bq-dihydroxypropyltetrahydroquinoline, N-fiq dihydroxypropyl 7- methoxytetrahydroquinoline, N-Bfl dihydroxypropyl 5- acetylaminotetrahydroquinoline, N-fi-hydroxyethyl -2,2,4- trimethyltetrahydroquinoline, N-[i-hydroxyethylbenzomorpholine and N-p,'y-dihydroxypropyl-5-acetylaminobenzomorpholine.

Further coupling components of the aniline series that may be mentioned are those containing a quaternatable or quaternated group, for example, N-methyl-N,2-dimethylaminoethylaniline, N,2-(N'-ethyl-N-phenyl) aminoethylpyridinium chloride and also, for example, compounds of the formulae Diazotizable amines can also be mentioned as coupling components of the aniline series, for example, 1-amino-3- methylbenzene, 1-amino-2-methoxy 5 methylbenzene, l-amino-naphthalene, and so forth; when used, aminoazo dyestufls are formed that can be diazotized and then coupled with the coupling components specified above to form diazo or polyazo dyestufis.

Finally, there may also be mentioned coupling components having acid hydrogen atoms, for example malodinitrile, phenylsulphonylacetonitrile, cyanoacetic acid methyl ester, cyanoacetic acid ethyl ester, cyanoacetic acid butyl ester, 4,5-dimethyland 4,5-dipheny1-imidazole.

The term coupling as used herein also includes the so-called oxidative coupling in which the diazonium compound of the diazo component is replaced by a corresponding hydrazine or hydrazone. By the process of oxidative coupling the quaternated compounds can also be obtained in one step, in this case, the benzthiazolium compounds.

The following scheme illustrates how coupling and simultaneous quaternation to form a monoazo dyestuff takes place:

Suitable dehydrogenating or oxiding agents are, for example, atmospheric oxygen, hydrogen peroxide, hypochlorites, persulphates, perborates, iron(III) salts, copper (III) salts, mercury(II) salts, lead(IV) salts and cerium (IV) salts and hexacyanoferrates(III); if necessary, oxygen carriers may also be used concomitantly, for example, heavy metals and the salts thereof.

The hydrazones can be prepared according to known methods [R. Reimschneider and S. Georgi, Monatshefte fiir Chemie, vol. 91, 623 (1960); S. Hiinig et al., Angewandte Chemie, vol. 70, 215 (1958); vol. 74, 818 (1962); vol. 80, 343 (1968); Chimia, vol. 15, 133 (1961); H. Baumann and H. Dehnert, Chimia, vol. 15, 163 1961)].

Diazotization of the diazo components specified can be carried out, for example, with a mineral acid and sodium nitrite or, for example, with a solution of nitrosylsulphuric acid in concentrated sulphuric acid, according to the position of the amino group concerned.

Coupling can also be carried out by known methods, for example, in a neutral to acid medium, if necessary, in the presence of sodium acetate or a similar buffer that influences the rate of coupling, or a catalyst,'for example, dimethylformamide, pyridine or a salt thereof.

Coupling may also be effected with advantage by combining the components in a mixing nozzle. By this is meant a device in which the liquids to be mixed are combined in a comparatively small space, at least one of the liquids being conducted through a nozzle, preferably under pressure. The mixing nozzle can be constructed on the principle of a water-jet pump, and function in like manner, the delivery of one of the liquids in the mixing nozzle corresponding to the delivery of water in a Water-jet pump, and the delivery of the other liquid into the mixing nozzle corresponding to the compound in the container of the water-jet pump to be evacuated. The latter delivery of liquid can also be effected under pressure.

However, other devices can also be used to elTect speedy and optionally, continuous mixing in a small space.

The dyestufls can be quaternated by virtue of the nitrogen atom in the benzthiazole ring and when the residue A or one of the residues R or R contains a quarternatable nitrogen atom, for example, the above mentioned heterocyclic amines of the formula DNH quaternation preferably being carried out as the last step. 1

Quaternation can be eifected by a treatment with esters of strong mineral acids or organic sulphonic acids, for example, dimethyl sulphate and diethyl sulphate, alkyl halides, for example methyl chloride, methyl bromide or methyl iodide, aralkyl halides, for example benzyl chloride, esters of low molecular weight alkane-sulphonic acids, for example, the methyl ester of methane-, ethaneor butane-sulphonic acid and the alkyl esters of (4- methyl-, 4-chloroor 3- or 4-nitro)-benzene sulphonic acid which form as anions halogen, sulphuric acid semiester, alkane or benzene sulphonic acid anions, preferably by heating in an inert organic solvent, for example, xylene, carbon tetrachloride, ortho-dichlorobenzene or nitrobenzene. However, other solvents may also be used, for example acetic anhydride, dimethylformarnide, acetonitrile or dimethyl sulphoxide. The quaternated dyestuffs preferably contain as anion Y- the residue of a strong acid, for example, the residue of sulphuric acid or semi-esters thereof, or a halide ion; however, they can also be used as double salts, for example, with zinc chloride, or as free bases.

The new water-insoluble dyestuffs, mixtures thereof and mixtures of these dyestufis with other azo dyestulfs are eminently suitable for dyeing and printing leather, wool, silk and in particular, synthetic fibres, for example acrylic and acrylonitrile fibres, polyacrylom'trile fibres and copolymers of acrylonitrile and other vinyl compounds, for example acrylic esters, acrylic amides, vinylpyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate and of acrylonitrile block copolymers, fibers made of polyurethane, basified polyolefines, for example polypropylene, cellulose triacetate and secondary acetate fibres and especially fibres made from polyamides, for example nylon 6, nylon 6.6 or nylon 12, and also fi'bres made from aromatic polyesters, for example, fibres made from terephthalic acid and ethylene glycol or 1,4 dimethylcyclohexane, and copolymers of terephthalic and isophthalic acid and ethylene glycol.

This invention therefore also provides a process for dyeing or printing textile materials based on synthetic fibres, especially polyester fibres, or when the dyestuffs are quaternated, acrylic fibres, wherein there are used dyestuffs of the formula in which A reperesents an aryl residue that may be substituted, X represents a sulphur atom or preferably an oxygen atom and B represents the residue of a coupling component that is free from acidic groups imparting solubility in water.

When dyeing is carried out in an aqueous liquor, the water-insoluble dyestuffs are advantageously used in a finely divided form and dyeing is carried out in the presence of a dispersing agent, for example sulphite cellulose waste liquor, or a synthetic detergent, or a combination of different wetting and dispersing agents. 'Prior to dyeing, it is generally advantageous to convert the dye stuff into a dyeing preparation that contains a dispersing agent and the finely divided dyestuif in a form such that a fine dispersion is formed when the preparation is diluted with water. Such dyestufi' preparations may be obtained in known manner, for example, by grinding the dyestuff in a grinding device in the dry or wet state in the presence or absence of a dispersing agent.-

To obtain stronger dyeings on polyethylene terephthalate fibres it is advantageous to add a swelling agent to the dyebath, or to carry out the dyeing process under superatmospheric pressure at a temperature of above 100 C., for example at 120 C. Suitable swelling agents are aromatic carboxylic acids, for example salicylic acids, phenols, for example orthoor para-hydroxydiphenyl, aromatic halogenated compounds, for example ortho-dichlorobenzene or diphenyl.

To fix the dyestulf, the padded polyester fabric is heated to a temperature above 100 C., for example to a temperature between 180 and 210 0., preferably after drying, for example in a current of warm air.

The dyeings obtained in accordance with this process can be subjected to an after-treatment, for example by heating with an aqueous solution of a non-ionic detergent.

The dyestuffs may also be applied by printing processes. In this method of application a printing paste, for example, in used which contains the finely divided dyestuif as well as the adjuvants normally used in printing, for example, wetting and thickening agents.

The process yields strong dyeings and prints possessing good properties of fastness.

The dyestufifs of the invention are also specially suitable for dyeing and printing polypropylene fibres modified with nickel, the dyestuffs used preferably being those that contain in ortho-position to the azo group, groups of atoms capable of forming complexes, for example hydroxy, carboxyl, carbalkoxy and alkoxy groups.

10 Dyestuifs that are specially suitable for dyeing polypropylene modified with nickel are those of the formula in which A has the meaning given above and B represents a coupling component containing in ortho-position to the azo group a group capable of forming a complex.

The new water-insoluble dyestulfs can also be used in the spin-colouration of polyamides, polyesters and polyolefins. The polymer to be coloured in advantageously mixed with the dyestuff in the' form of a powder, grains or chips, in the form of a solution ready for spinning or in the form of a melt, the dyestuif being in the dry state or in the form of a dispersion or solution in a solvent that may be volatile. After the dyestufi has been homogene ously dispersed in the polymer solution or melt, the mixture is processed in known manner into fibres, yarns, monofilaments, films and so forth by casting, molding or extruding.

The new water-soluble quaternated dyestuffs or dyestuff salts are suitable for dyeing and printing a very wide variety of synthetic fibres, for example polyvinyl chloride, polyamide, polyurethane and especially polyacrylic fibres.

The following examples illustrate the invention, the parts and percentages being by weight, unless otherwise stated.

EXAMPLE 1 6.1 parts of Z-aminobenzthiazolyl 6 sulphonic acid phenyl ester are stirred overnight with 50 parts of phosphoric acid. The next day, the batch is cooled to l4 C. and 1.5 parts of pulverized sodium nitrite are added. A yellow suspension is obtained which is added, while cooling and stirring, to a solution of 4.86 parts of N cyanoethyl N cyanoethoxyethylaniline in 250 parts of ethyl alcohol. The batch is stirred for 3 hours, diluted with parts of ice, filtered, and the filter residue is washed successively with 80% alcohol, 50% alcohol and water until free from acid. The dyestulf of the formula is obtained in a good yield. It dyes secondary acetate, triacetate and polyester fibres a red shade possessing excellent properties of fastness.

The dyestuffs of the formula listed in the following table may be obtained by diazotization and coupling in accordance with this example. The dyestuffs obtained dye secondary acetate, triacetate, polyamide and polyester fibres the shades indicated in the last column.

.oQ m m m ....,...,.......,.w.-........ 95% mm 2 2mm H 5 8m l 5 EM Z055 zo m o mo o omz m OK 6Q ZOQWNOI. N NO O 552 mm Sham TU O e o m o o mox mov n 2056 m m WY- Q mooooqfio 5000056 "moo 0 6Q OJw O WI. m 126D? 2. 25m m 8% m m m0 0 32.? ED000055 E OOOOOE O G O Z mmoo c 0 Em mo o m o "M0 056 6 .mn m E OOOOJH O HW OOOO HH O mOO 5.1-1--.. obona mm madm 0 65 mo 50 mofiooomnz "mo o mo mo o omz 6 m Z065 m m 8 J. 6 m 2056 055 Z056 6 m 6 m "m0 O HH O zo m o m HT] All-1..., o o ma 0 am 1N 6 m 5000055 5000055 o oo 25am m JH MW mm 4 6 m mo 0 ofi o m o mo m Em mo 0 o 056 m o mo m mm Em 656 656 m m .6596 6 m 2 7 O e omzfi o o m o o o x mov Em zofi o m m 63m E0 E0 0055 m m 8 3 M mo o m o V 0 2056 m m 8 m mm SZ O EO o w o o mz oo mz Em "mo ofi o N m a OLHBLET 6 m 2056 M m 8 a umol Em O Z056 m 5 w 3 :EQJH N 6 w n we e56 EG mooomz 7 m a an Z056 056 E0 m mo o 8 8 m movmo mo 00 W M m m .7 o w o o mzo a mo m Em mo E0 E6 M m 7 a W Eo o 6 m 2056 m m 3 w NN 5 moooofimo zofi o fioooomz 7 m a m 8m 50 ofl o zofi o 056 m m m -8 3 mm ZOE 6 zo m o U m 8 w -2 W 6 o m o o o mo 62 mo 00 056 moooofifi mofiooomz m7 E0 0 S m Em W056 6 6 m o o omz m mo 2 2 a m 5 26mm em 5 W V N 62 v v EXAMPLE 2 6.4 parts of Z-aminobenzthiazolyl-6-sulphonic acid-(3'- methylphenyl ester) are stirred overnight with parts of phosphoric acid. The next day, the batch is cooled to 14 C. and 1.5 parts of pulverized sodium nitrite are added. A yellow suspension is obtained which is added, while cooling and stirring, to a solution of 2.62 parts of Z-methylindole in 150 parts of methanol. The batch is stirred for 3 hours, diluted with parts of ice, filtered, and the filter residue is washed successively with 80% methanol and 50% methanol and then with water until free from acid. The dyestuff of the formula 16 of 85% phosphoric acid. The next day, the batch is cooled to 14 C. and 1.5 parts of pulverized sodium nitrite are added. A yellow suspension is obtained which is added, while cooling and stirring, to a solution of 9.8 parts of 3 dibromopropionylamino-N,N-diacetoxyethylaminobenzene in 250 parts of methanol. The batch is stirred for 3 hours, diluted with parts of ice, filtered, and the filter residue is washed successively with 80% methanol and 50% methanol and then with water until free from acid. The dyestufi of the formula v 3 CN=N Nwmidooom -oso S NHCOCH-CH: Iii: 1 31 is obtained in a good yield. It dyes secondary acetate, triacetate, polyamide and polyester fibres a violet shade possessing excellent properties of fastness.

The dyestuffs of the formula listed in the following table may be obtained by diazotization and coupling in accordance with this example. The

No. I III 2- mino-G- hen 10x sul hon l-benzthiazole-.. 2-methy1-5-ch1oroindole. Yellow. 2 a do p y y p y 2-methy1-7-chloroindole. Do. a do. 2-methy1-5-bromolndo1e- Do. 4 do 2 fi-dlmethylimlole Do. 5 2-annno-6-(3-methoxyphenyl-oxysulphonyl)-benzthiazole N-B-eyanoethyl-l,2,3-tetral1ydroind0le D0. 6 (10.... 2,6-dlmethylindole Do. 7 do- 1-methyl-2-phenylindole Do. do 1,2-glme1tih3lii1d0le go. amino-fien 1 hen l-ox sul hon 1 enzthlazole Z-p any 11 0e 0. d0 KB. X- y i l-pheny1-3-methyl-5-an1ln0pyraz0le Do. 11 do l-phenyl-3-methyl-fi-pyrazolone Do.

EXAMPLE 3 6.7 parts of 2-aminobenzthiazolyl-6-sulphonic acid-(3'- methoxyphenyl ester) are stirred overnight with 50 parts dyestuffs obtained dye secondary acetate, triacetate, polyamide and polyester fibres the shades indicated in the last column.

Example of dyeing procedure A mixture comprising the following components is then prepared by means of a high-speed stirrer:

10 parts of a knitted fabric made from nylon 6.6 parts of the above paste ("Helanca) are entered at 30 C. into a dyebath con- 310 parts of ld water sisting of 0.2 part of 80% acetic acid and 2 parts of a r 50 parts of urea aqueous dispflsion of the compound Obtained 111 0 500 parts of a 5% aqueous sodium alginate solution accordance with Example 3 in 400 parts by volume of p 40 parts of ammonium sulphate water, the pH of the bath being 4 to 5. The dyebath is brought to the boil within 45 minutes and dyeing is 1000 parts i; A boiling is continued for a further 30 minutes. The textile the pnntmg paste so Obtamed After the fabnc dried steamed for 30 minutes rinsed in cold water material is then well rinsed with water and dried. A Is o brilliant violet dyeing possessing a high proportioning of i forzzo mmute? 60 m if Solutlog f i non-extractable dyestutf is obtained. mg to grams 0 t e con ensa'lon pro uc O 1: mols of ethylene oxide and 1 mol of nonylphenol per gg giig g z zifiig l gigg gf ifg g g f gig 0 litre of water, and then rinsed with cold water. A bluish an d 40 parts of sodium dinaphthylmethane disulphonate. green punt Possessmg very good propemes of fasmess is obtained.

EXAMPLE 5 6.1 parts of 2-aminobenzthiazolyl-6-sulphonic acid phenyl ester are stirred overnight with 50 parts of 85% Parts of zfammobenth1aZlyl'6'Sulphmc acid phosphoric acid. The next day, the batch is cooled to phenyl ester are stirred overnight with 50 parts of 85% and 15 parts of pulverizedsodium nitritqaflrve E acid The next l l 1S to added. A yellow suspension is obtained which is added, and verlzed mimte while cooling and stirring, to a solution of 7.2 parts of added. A yellow suspension is obtamed which, while cool- N dimethyl N hexyl N l3 (ethy1pheny1anfino) ethy1 mg and l' is run mm a solutlon 9 1 Parts of amino-ammonium bromide in 150 parts of 80% methf a m 75 Parts of ethyl alcohol Wlth s1mu ltaneus anol. The batch is stirred for 3 hours, diluted with 150 addition of an NaOH solut1on. The batch is stlrred for Parts f ice, the d t if is salted out with sodium 1 3 hours, 150 parts of ice are added, the batch is filtered and the filtered residue is washed successively with 80% EXAMPLE 4 the formula CzHz CH -Ox .w G o.H.-N-(oH2).on,

Br on,

alcohol and 50% alcohol and then with water until free is obtained in a good yield. It dyes polyacrylonitrile from acid. The dyestutf of the formula fibres a red shade possessing excellent properties of fast- N 11$SS. R The dyestuffs of the formula C-N=N Q is obtained in a good yield. It yields bluish green dyeings C'N=N-B and prints possessing excellent properties of fastness on A- nickel-modified polypropylene. -It dyes polyester fibres an 5 orange shade possessing excellent properties of fastness.

Printing procedure 1 part of the dyestutf obtained in accordance with given in the following table may be obtained by diazotiza- Example 4 is ground in a ball mill together with 1 part tion and coupling in accordance with this example. The of l,1'-dinaphthylmethane-2,2'-disulphonic acid to form shades they produce on polyacrylonitrile fibres are india fine aqueous paste having a dyestufi content of 10%. cated in the last column.

No. A Shade 1 C2H4OCH3 G3 Red:

-N\ 01117503 7 H CzHr-N 2 0 CH: G9 Violet:

O-S O:-

NHCHzGHz-N 01 I NHGO CH ride and isolated by vacuum filtration. The dystuff of TABLEContinued No. A B Shade 3 N(CH:)3 (3H3 63 Red. H; N

C2H4OCO 6 CHaSO4 O N CHaSO| CzH4CN 4..-..; N11, ea Red." Q-o-s O2' 6 H(CH3)2 CHaSO;

S OzNII CH1)-N CH3) a a 5..'.".;'.'..::: CH3 Yellow.

-o-s O2-- HO- N Ha N -NHCO(CH2)2N(CH:)3

EXAMPLE 6 6.7 parts of 2-aminobenzthiazolyl-6-sulphonic acid-(2, 4'-dimethylphenyl ester) are stirred overnight with 50 parts of 85% phosphoric acid. The next day, the batch is cooled to -14 C. and 1.5 parts of pulverized sodium nitrite are added. A yellow suspension is obtained which is added, while cooling and stirring, to a solution of 3.76 parts of N-cyanoethyl-N-ethyl-meta-toluidine in 250 parts of methanol. The batch is stirred for 3 hours, filtered the filter residue is Washed successively with 80% alcohol and 50% alcohol and then with water until face from acid, and then dried.

5.5 parts of the dyestuif so obtained are dissolved in 50 parts of dimethylformamide; 2.5 parts of dimethyl sulphate are added and the batch is stirred for 1 hour at 130 C. The solvent is then evaporated, the residue is dissolved in hot water, and the dystuff of the formula is salted out with sodium chloride and isolated by filtration. It dyes polyacrylonitrile fibres a bluish red shade possessing excellent properties of fastness.

I claim:

1. An azo dyestuif free from acidic groups imparting solubility in water of the formula n-l .A-O-SO CN=NB in which A represents phenyl or phenyl substituted by C -C -alkyl, C -C -alkoxy, cyclohexyl, phenyl, dimethylaminomethyl, di(C -C -alkyl)amino, phenoxy, C -C fatty acid acylamino, benzoylamino, C C -alkoxycarbonylamino, C C -alkylaminocarbonylamino and NHCONH R is C -alkyl or benzyl, R is hydrogen or methyl, n is 1 or 2, Y'- is an anion, and B is a coupling component selected from the group consisting of a phenol, meta-cresol, para-cresol, o.--naphthol, fl-naphthol, 4-meth0xy-l-hydroxynaphthalene, 2-hydroxy-8-methylsulphonylaminonaphthalene, 2-hydroxynaphthalene-3-carboxylic acid anilide, Z-hydroxy-8-acetylarninonaphthalene, 1-hydroXynaphthalene-3-sulphonemethylene-ether-4, 2-hydroxynaphthalene-fi-sulphonamide, 2-hydroxynaphthalene-G-sulphonic acid dimethylamide, l-hydroxy-5,8-dichloronaphthalene, N43-dimethylaminoethyl-2-hydroxynaphthalene-3-carboxylic acid amide, 1- or 2-naphthylamine, 2-phenylaminonaphthalene, 1-dimethylaminonaphthalene,

21 1-butyl-3-methylpyrazolone-5, 1-hydroxyethyl-3-methylpyrazolone-S, 1-cyanoethyl-3-methylpyrazolone-5, l-(ortho-chlorophenyl)-3-methylpyrazolone-5, 3-carbomethoxypyrazolone-5, 8-hydroxyquinoline, 1-methyl-4-hydroxyquinolone-2, N-ethyl-3-hydroxy-7-methyl-1,2,3,4-tetrahydroquinoline, barbituric acid, 1,3-indandione, 1,8-naphthindandione, dimedone, acetoacetic acid anilide, meta-hydroxy-N,N-diethylaniline, 3-hydr0xy-4'-methy1diphenylamine, hydroquinone-monomethylether, aeetyl acetone,

S-hydroxybenzthiazole, 1,Z-diphenylpyrazolidine-3,5-dione, 2,3,4-tetrahydroquinoline, N,,B-cyanoethy1- or N-p-hydroxyethyltetrahydroquinoline, N-l ,'y-dihydroxypropyltetrahydroquinoline, N-,B,'y-dihydroxypropyl-7-methoxytetrahydroquinoline, N-B,'y-dihydroxypropyl-5-acetylaminotetrahydroquinoline, N-p-hydrOXyethyl-Z,2,4-trimethyltetrahydroquinoline, N-[i-hydroxyethylbenzomorpholine, N-B,'y-dihydroxypropyl-5-acetylaminobenzomorpholine,

and those of the formula in which d represents hydrogen, halogen, lower alkyl, lower alkoxy, lower alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, cyclohexylmethyl or benzyl, c is the same as d or C -Cl -acylamino, styryl carbonylamino B-chlorophenoxy, phenylureido, phenylsulfonylamino, N-ethyl-N-isopropylacetyl, m,B-dibromopropionylamino, trifluoromethyl, methanesulfonylamino, ethanesulfonylamino, methoxycarbonylamino,

R and R each is hydrogen'or lower alkyl optionally interrupted by oxygen, which may be substituted by chlorine, phenyl, cyano, C -C -alkyl, C -C -fatty acid acylamino, hydroxy, C -C -fatty acid acyloxy, benzoyl, methoxybenzoyl, phenoxybenzoyl, benzyloxy, nitrophenyl, nitrophenoxy, B-cyanoacetoxy, methoxy, carboxy, benzoylamino, difluorotriazinyl, pyridyl, C -C '-alkyloxycarbonyl, methylcarbamyloxy, phenylcarbarnyloxy, di- (C -C -alkynamino, alkyl-ammoniurn, pyridinium and pyridinium carbonyloxy, R can be also phenyl or 4-ethoxyphenyl, and R and R together may be 2. An azo dyestutf as claimed in claim 1 wherein B is a coupling moiety of the formula in which d represents hydrogen, halogen, lower alkyl, lower alkoxy, lower alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, cyclohexylmethyl or benzyl, c is the same as d or C C -acylamino, styryl carbonylamino, B-chlorophenoxy, phenylureido, phenylsulfonylamino, N-ethyl-N-isopropylacetyl, u,fl-dibromopropionylamino, trifluoromethyl, methanesulfonylarnino, ethanesulfonylamino, methoxycarbonylamino,

A-O-SO in which A represents phenyl or phenyl substituted by C -C alkyl, C -C alkoxy, C -C cyclohexyl, phenyl, dimethylaminomethyl, di(C -C alkyl)amino, phenoxy, C -C fatty acid acylamino, benzoylamino, C -C alkoxyearbonylamino, C -C alkylaminocarbonylamino and --NHCO--NH B is a coupling moiety of the formula in which d represents hydrogen, halogen, lower alkyl, lower alkoxy, lower alkylmercapto, phenyl, phenylmercapto, phenoxy, cyclohexyl, cyclohexylmethyl or benzyl, c is the same as d or C -C acylamino, styryl carbonylamino, B-chlorophenoxy, phenylureido, phenylsulfonylamino, N-ethyl-N-isopropylacetyl, a,;8-dibromopropionylamino trifiuoromethyl, methanesulfonylamino, ethanesulfonylamino, methoxycarbonylamino,

R and R each is hydrogen or lower alkyl optionally interrupted by oxygen, which may be substituted by chlorine, phenyl, cyano, C -C alkyl, C -C fatty acid acylamino, hydroxy, C -C fatty acid acyloxy, benzoyl, methoxybenzoyl, phenoxybenzoyl, benzyloxy, nitrophenyl,

wherein each of the residues c and d represents hydrogen, methyl, ethyl, methoxy, ethoxy, phenyl, phenylthio or phenoxy and in which 0' can also represent C acylamino.

5. A dyestutf of the formula CzH -O-C H CN 6. A dyestulf of the formula FMFO 7. A dyestulf of the formula 8. A dyestuff of the formula 9. A dyestufi. of the formula References Cited UNITED STATES PATENTS 3,418,310 12/1968 Dale III et a1. 260-158 JOSEPH REBOLD, Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R.

826, 41 B, 41 D; 260146 R, 153, 155, 239.9, 294.8 R, 294.9, 295 AM, 305, 310 A, 465 D, 556 AR UNITED STATESPATENT- OFFICE CERTIFICATE OF CORRECTION Patent: No. 3,686,162 Dated August 22, 1972 Inventor s) KLAUS ARTZ It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 23, left-hahd formula should read Column 23, bottom formula should read UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N 5,686,162 Dated August 22 1972 Inventor(s) KLAUS ARTZ PAGE 2- It is' certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2 claim 9 formula. should read Sined and sealed this 6th dayof August 1974.

(SEAL) Attest:

McCOY M. GIBSON, JR. 7 c. MARSHALL DANN Attesting Officer Commissioner of Patents 

